Containers—such as, for example, bottles or jars, serve inter alia as a storage location for liquids in the cosmetics and dermatological sector. The bottles here are produced in particular from a flexible plastic, so that gentle pressure on the body of the bottle is sufficient to expel the liquid in the bottle out of the opening.
The known plastic bottles for shower formulations, liquid soaps and shampoo may be mentioned by way of example here, without this list being complete. Bottles which can be closed with a screw lid are preferred.
The bottles or containers are often produced by the extrusion blow molding process.
U.S. Pat. No. 3,892,829 discloses a process and a device for the production of flat bottles from an extruded parison which is preblown in an intermediate mold and only then is transferred into a final blow mold, the mold cavity of which has the contour of the flat bottle to be produced.
DE 37 02 844 A1 discloses a process which follows this principle and an extrusion blow molding machine which operates thereby. In this, a parison of plastic is freely extruded, taken up in an intermediate mold and blow-molded there into a rotationally symmetric intermediate molding. This intermediate molding, which consequently has a circular cross-section at every height, already has approximately the length (height) of the flat bottle to be produced, and has in its main sections (base, body, neck) a circumference which is more or less approximately the corresponding circumferences of the flat bottle. The latter is shaped by transferring the intermediate molding into a final blow mold, such as is known, for example, from DE 27 20 448 C2.
This technique of production, which is largely waste-free and accordingly free from pinch-off welds, of flat bottles of substantially uniform wall thickness has proved itself.
In EP 0 688 658 A1, the intermediate molding is supported (mechanically) from underneath at least during transfer from the intermediate mold into the final blow mold. The intermediate molding is supported by an additional movable mold part at least during transfer from the intermediate mold into the final blow mold. This mold part can advantageously match the base contour of the intermediate molding. As a rule the molding must be displaceable in the vertical direction, so that closing of the final blow mold is not impeded.
Massage applicators have also be known for a long time. They exist in the most diverse shapes and materials. They can be made of plastics or naturally occurring materials.
A massage device which can be controlled electrically and is integrated into seating furniture, such as an easy chair or the like, is already known. In this known massage device one or more massage heads are arranged underneath the seat cover. These massage heads are driven electrically by electric motors, so that they are set in motion and a person sitting on the seating furniture can be massaged in an appropriate place by means of the massage head.
A massage device in which massage pins extend from a ball of plastic distributed in the radial direction over the ball surface, so that for massage this ball can be rolled over the surface to be massaged or the human body is furthermore known.
Plastic massage applicators can have the most diverse shapes. Roller/ball applicators and pin applicators are known.
In roller or ball applicators movable balls are held in a suitable direction and a pure pressure massage is achieved in this manner. The pressure massage is very skin-friendly since the frictional resistance is reduced to a minimum.
Pin applicators of rubber or flexible plastic show an increased friction. This increased friction intensifies the massage effect in the upper layers of skin, but can also lead to skin irritations on sensitive areas of skin. Generally, a more intense massage effect is achieved by massage with a pin applicator. At the same time massage with a pin applicator also leads to higher mechanical stress on the skin and the underlying tissue and therefore to an increased blood circulation in the skin.
The increased blood circulation and the massage of the subcutaneous tissue leads to a consolidation of the subcutaneous tissue. This consolidation leads to an improvement in the appearance of the skin and in this way prevents cellulite or counteracts it.
The points mentioned for massage applicators of plastic also apply generally to massage applicators of naturally occurring materials, such as, for example, wood. However, in the case of these applicators of naturally occurring substances there are also additionally special forms which are made of, for example, braided sisal rope or similar materials. On these applicators the rough surface of the naturally occurring substances is used for the massage.
Even in a simple water bath without addition of surfactants a swelling of the horny layer of the skin initially occurs, the degree of this swelling depending, for example, on the duration of the bath and its temperature. At the same time water-soluble substances, e.g. water-soluble dirt constituents, but also endogenous substances of the skin which are responsible for the water-binding capacity of the horny layer, are washed off or out. In addition, skin oils are dissolved and washed out to a certain extent by endogenous surface-active substances of the skin. After initial swelling, this causes a subsequent significant drying out of the skin, which can be intensified further by wash-active substances.
In healthy skin these processes are in general inconsequential, since the protective mechanisms of the skin can easily compensate such mild disturbances in the upper layers of skin. However, already in the case of non-pathological deviations from the normal state, e.g. due to environment-related wear damage or irritation, damage caused by light, senile skin etc., the protective mechanism of the skin surface is impaired. Under certain circumstances it is then no longer capable of fulfilling its task by its own means and must be regenerated by external measures.
Liquid shower preparations in the form of syndets (synthetic detergents) have been known for a long time. They are substantially surface-active substances or substance mixtures which are offered to the user in various formulations. Formulations of such a type are in general distinguished by a more or less high water content, but can also be in the form of, for example, a concentrate. Nowadays these are chiefly soap-free formulations with a pH of below 7. The development of such products was first possible with the discovery of synthetic surfactants. Since this time these products have been frequently further developed and there is a very large field of the prior art. These wash-active substances have, as is known to the expert, barrier-damaging actions. Due to the prolonged application more surfactants also remain on the skin after rinsing off with water. The barrier-damaging action of surfactants and the remaining on the skin after rinsing off has already been described in detail in our Application “Process for the preparation of particularly skin-friendly cosmetic or dermatological cleaning formulations” (DE 199 60 767 A1). In particular, the intensive application of the shower product by means of massage leads to an increased risk of irritation. The top layers of skin are detached by the massage and the skin barrier weakened. As a result, the wash-active substances can penetrate into lower layers of skin and cause irritation.
The fluid formulations are preferably emulsions, suspensions, colloids, dispersions gels or solutions.
Gelatinous shower formulations can also be formulated without gel-forming agents, since certain surfactant mixtures thicken on addition of salts.
In the technical sense, gels are understood as: relatively dimensionally stable, easily deformable disperse systems of at least two components, which as a rule comprise a—usually solid—colloidally divided substance of long-chain molecular groupings (e.g. gelatins, silica, polysaccharides) as the structure-forming substance and a liquid dispersing agent (e.g. water). The colloidally divided substance is often called a thickener or gelling agent. It forms a three-dimensional network in the dispersing agent, it being possible for individual particles present in colloidal form to be linked to one another more or less firmly via electrostatic interaction. The dispersing agent, which surrounds the network, is distinguished by an electrostatic affinity for the gelling agent, i.e. a predominantly polar (in particular: hydrophilic) gelling agent preferably gels a polar dispersing agent (in particular: water), whereas a predominantly non-polar gelling agent preferably gels non-polar dispersing agents.
Strong electrostatic interactions, which are realized, for example, in hydrogen bridge bonds between the gelling agent and dispersing agent, but also between dispersing agent molecules among one another, can lead to high crosslinking also of the dispersing agent. Hydrogels can comprise almost 100% water (in addition, for example, to approximately 0.2-1.0% of a gelling agent) and thereby entirely have a solid consistency. The water content here is present in ice-like structural elements.
In the field of cosmetics and pharmaceuticals formulation, lipogels and oleogels (from waxes, fats and fatty oils) and carbogels (from paraffin or petrolatum) are furthermore also usual. In practice, a distinction is made between oleogels, which are in a practically anhydrous form, and hydrogels, which are practically fat-free. Gels are usually transparent. In the field of cosmetics or pharmaceuticals formulation, gels are as a general rule distinguished by a semi-solid, often fluid consistency.
So-called surfactant gels are furthermore conventional formulations of the prior art. These are understood as meaning systems which, in addition to water, have a high concentration of emulsifiers, typically more than approximately 25 wt. %, based on the total composition. If oil components are solubilized in these surfactant gels, microemulsion gels, which are also called “ringing gels” are obtained. Cosmetically more elegant microemulsion gels can be obtained by addition of nonionic emulsifiers, for example alkyl polyglycosides.
Emulsions are metastable two- or multiphase systems in which the individual phases are present in the liquid state. The most usual emulsions are O/W (oil-in-water) and W/O (water-in-oil) emulsions. Rarer presentation forms are multiple emulsions, that is to say those which in the droplets of the dispersed (or discontinuous) phase in their turn contain droplets of a further dispersed phase, e.g. W/O/W emulsions and O/W/O emulsions. In simple emulsions, in the one phase finely disperse droplets of the second phase enclosed by an emulsifier shell (water droplets in a W/O emulsions or lipid vesicles in O/W emulsions) are present. The droplet diameters of the usual emulsions are in the range from approximately 1 μm to approximately 50 μm. Such “macroemulsions” are, without further coloring additives, milky white in color and opaque. Finer “macroemulsions”, the droplet diameters of which lie in the range from approximately 10−1 μm to approximately 1 μm, are, again without coloring additives, bluish-white in color and non-transparent.
Micellar and molecular solutions with particle diameters of less than approximately 10−2 μm appear clear and transparent.
The droplet diameter of transparent or translucent microemulsions, on the other hand, is in the range from about 10−2 μm to about 10−1 μm. Such microemulsions are usually low-viscosity. The viscosity of many microemulsions of the O/W type is comparable to that of water.
Emulsions represent by far the most important product type in the field of skin care compositions or in the field of cosmetic and/or dermatological formulations. Emulsions are disperse two- or multiphase systems, cosmetic emulsions comprising at least one fatty phase (fats and mineral oils, fatty acid esters, fatty alcohols etc.) and at least one aqueous phase (water, glycerol, glycols etc.) which are distributed in one another in the form of very fine droplets with the aid of emulsifiers. If the two liquids are water and oil and oil droplets are present finely divided in water, this is an oil-in-water emulsion (O/W emulsion, for example milk). The basic character of an O/W emulsion is imposed by the water. In a water-in-oil emulsion (W/O emulsion, for example butter) the principle is the reverse, the basic character here being determined by the oil.
The oily phase is advantageously chosen from the group of esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols, from the group of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unsaturated alcohols, from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides. Any desired blends of such oil and wax components can also advantageously be employed in the context of the present invention. It may also be advantageous, where appropriate, to employ waxes, for example cetyl palmitate, as the sole lipid component of the oily phase.
The oily phase can advantageously have a content of cyclic or linear silicone oils, for example cyclomethicone (octamethylcyclotetrasiloxane) or consist entirely of such oils, although it is preferable to use an additional content of other oily phase components in addition to the silicone oil or the silicone oils. The emulsions described here and in the following can thus correspondingly be produced as silicone emulsions with use in part or entirely of silicone oils. Corresponding statements apply to the other oil-containing formulations.
The expert knows of a large number of possibilities for formulating stable O/W formulations for cosmetic or dermatological use, for example in the form of creams and ointments which are spreadable in the range from room to skin temperature, or as lotions and milk, which are rather fluid in this temperature range and can be stored particularly favorably with the containers according to the invention.
The stability of emulsions depends inter alia on their viscosity, in particular on the viscosity of the external phase. An emulsion becomes unstable if the finely dispersed particles agglomerate again into larger aggregates and the droplets which touch each other merge. This process is called coalescence. The process of coalescence proceeds more slowly the more viscous the external phase of the emulsion.
O/W emulsions are accordingly as a rule stabilized by thickeners, which increase the viscosity of the aqueous phase. Polyacrylates (Carbomer) and further organic thickeners, for example, are suitable for this. A disadvantage of this method of improving the stability is the sensitivity of these formulations to electrolytes. Furthermore, chiefly higher-viscosity formulations (such as creams or ointments) are of course to be prepared in this manner.
Emulsions of “liquid” (=fluid) consistency are used in cosmetics for example as a care, cleaning, facial or hand lotion. As a rule, they have a viscosity of about 2,000 mPa·s up to about 10,000 mPa·s. Particular attention is to be paid to the stability of fluid emulsions, since the considerably higher mobility of the particles promotes a faster coalescence.
Conventional emulsifiers can be classified into ionic (anionic, cationic and amphoteric) and nonionic according to their hydrophilic molecular part: The best-known example of an anionic emulsifier is the soaps, as the water-soluble sodium or potassium salts of saturated and unsaturated higher fatty acids are usually called.
Important representatives of the cationic emulsifiers are the quaternary ammonium compounds.
The hydrophilic molecular part of nonionic emulsifiers often consists of glycerol, polyglycerol, sorbitans, carbohydrates or polyoxyethylene glycols and is usually linked to the lipophilic molecular part via ester and ether bonds. This usually consists of fatty alcohols, fatty acids or iso-fatty acids. The lipophilicity and hydrophilicity of emulsifiers can be varied within wide limits by varying the structure and the size of the polar and the nonpolar molecular part.
The correct choice of the emulsifiers is decisive for the stability of an emulsion. The characteristics of all the substances contained in the system are to be taken into consideration here. Considering skin care emulsions, for example, polar oily components and, for example, UV filters lead to instabilities. In addition to the emulsifiers, other stabilizers are therefore also used, these for example increasing the viscosity of the emulsion and/or acting as a protective colloid.
The use of the conventional emulsifiers in cosmetic or dermatological formulations is acceptable per se. Nevertheless, emulsifiers, as in the end any chemical substance, can cause allergic reactions or reactions based on hypersensitivity of the user in the individual case. There has therefore been no lack of attempts to reduced the amount of conventional emulsifiers to a minimum, and in the ideal case even completely.
A reduction in the amount of emulsifier required can be achieved, for example, if the fact that very finely divided solid particles have an additional stabilizing action is utilized. This results in a concentration of the solid substance at the oil/water phase boundary in the form of a layer, whereby merging of the disperse phases is prevented. It is not the chemical but the surface properties of the solid particles which are of essential importance here.
It is a relatively new technical development to stabilize cosmetic or dermatological formulations only by very finely divided solid particles. Such “emulsifier-free” emulsions are called Pickering emulsion after their inventor. One possibility of carrying out stabilization of solids in a cosmetic or dermatological formulation is, for example according to May-Alert (Pharmazie in unserer Zeit, vol. 15, 1986, no. 1, 1-7), to use emulsifier mixtures which comprise both anionic and cationic surfactants. Since insoluble, electroneutral compounds always precipitate out when anionic and cationic surfactants are brought together, an additional stabilization of solids in the sense of a Pickering emulsion can be achieved by controlled precipitation of these neutral surfactants in the oil/water interface.
WO 98/42301 A1 furthermore describes emulsifier-free finely disperse systems of the water-in-oil type which are stabilized by the addition of micronized, inorganic pigments chosen from the group of metal oxides, in particular titanium dioxide.
Emulsifier-free preparations based on so-called hydrodispersions have been accessible for the user for some time. Hydrodispersions are dispersions of a liquid, semi-solid or solid internal (discontinuous) lipid phase in an external aqueous (continuous) phase.
In contrast to O/W emulsions, which are distinguished by a similar phase arrangement, hydrodispersions however are substantially free from emulsifiers. Hydrodispersions, like emulsions, are metastable systems and tend to transform into a state of two discrete phases which are in themselves cohesive. In emulsions, the choice of a suitable emulsifier prevents phase separation.
In hydrodispersions of a liquid lipid phase in an external aqueous phase, the stability of such a system can be ensured, for example, by building up a gel structure, in which the lipid droplets are suspended in a stable manner, in the aqueous phase.
W/O lipodispersions are, in converse analogy, emulsifier-free finely disperse formulations of the water-in-oil type.
When a standard shower product was used with one of the abovementioned applicators the following negative product properties occurred in the past:                Shower product and massage applicator were not matched to one another, too intense or too weak a massage effect was achieved.        The intensity of the massage was not variable and therefore could not be adjusted to various skin zones.        The long action time of the shower product during the massage led to skin irritation.        Applicator was not matched to the shower product. Possibly, the applicator could be cleaned only poorly or not at all, or the surface was attacked or decomposed by the shower product.        Applicator and shower product were not matched to one another so that microbial contamination of the shower product and applicator could occur during inappropriate handling.        
A standard shower product and one or the abovementioned applicators always had to be used hitherto for a massage by means of an applicator under the shower, to date specific massage shower products have not yet been disclosed.